Novel phosphorus-containing compounds and flame retarded polymeric compositions therewith

ABSTRACT

The flammability of polymeric materials is substantially reduced or obviated by associating therewith novel halogen-containing phosphites, phosphates and phosphonates. Polymeric materials can be processed at elevated temperatures of the order of 250*-300*C. with certain of the phosphorus compounds.

wa tage Unites Statl Anderson et a1.

[ June 11, 1974 NOVEL PHOSPHORUS-CONTAINING COMPOUNDS AND FLAME RETARDEDPOLYMERlC COMPOSITIONS THEREWITH Inventors: James J. Anderson; WendellM.

Byrd, Jr.; Vasco G. Camacho, all of Richmond, Va.

Assignee: Mobil Oil Corporation, New York,

Filed: Mar. 2, 1972 Appl. No.: 231,368

Related 1.1.5. Application Data Division of Ser. No. 859,196, Sept. 19,1969, Pat. No. 3,706,821, which is a continuation-in-part of Ser. No.826,019, May 19, 1969, abandoned.

1U.S. CL... 106/15 FP, 260/D1G. 24, 260/457 P lint. Cl. C08f 45/58, C09d5/18, CO9k 3/28 Field of Search 106/15 FP, 16l8;

260/D1G. 24, 45.7 P, 95]; 2/461 Primary ExaminerAllan LiebermanAssistant Examiner-S. L. Fox Attorney, Agent, or Firm-Andrew L.Gaboriault [57] ABSTRACT The flammability of polymeric materials issubstantially reduced or obviated by associating therewith novelhalogen-containing phosphites, phosphates and phosphonates. Polymericmaterials can be processed at elevated temperatures of the order of250300C. with certain of the phosphorus compounds.

2] Claims, No Drawings NOVEL PHOSPIIORUS-CONTAINING COMPOUNDS AND FLAMERETARDED POLYMERIC COMPOSITIONS TI-IEREWITH RELATED APPLICATIONS:

This is a division, of application Ser. No. 859,196, filed Sept. 18,1969, now Pat. No. 3,706,821.

Application Ser. No. 859,196 is a continuation-inpart of our applicationSer. No. 826,019, filed May 19, 1969 which has been abandoned. Theprocess for preparing halogenated compounds described in applicationSer. No. 789,404, filed Jan. 6, 1969 which has been abandoned, can beused for the preparation of the halogen-containing phosphorus compoundsof this invention.

BACKGROUND OF THE INVENTION The present invention has to do with novelhalogencontaining phosphites, phosphates and phosphonates, and withflame retarded polymeric compositions containing the same.

It is known that certain halogen-containing, organic phosphoruscompounds are flame retardants for polymeric materials. Unfortunately, avariety of such compounds are not sufficiently stable to be used withcertain polymeric materials which are processed at relatively hightemperatures, for example 250300C. In

addition, many polymer compositions containing known flame retardantsare rendered nonflame retardant after exposure to environmental end-useconditions.

SUMMARY OF THE INVENTION In accordance with the present invention, thereare provided compounds represented by the general for mula and mixturesthereof,

wherein,

X is bromine or chlorine,

R is H, CH or CH X, provided that when one R is other than H, theadjacent R is H,

R is X, alkyl, haloalkyl, alkoxy. aryl, haloaryl or arylalkyl, whereinhalo is X,

R" is H or CH Q is ocnorrx, CHCHX,

l R l 1' alkyl, alkoxy, haloaryloxyalkyl haloarylpoly(oxyalkyl), whereinhalo is X, a is 0, 1 or 2, nis 1,2 or 3,

v is zero or 1,

w is zero, 1, 2 or 3, with the proviso that when w is zero, X is Br orcombinations of Br and Cl, and when w is l, 2 or 3, X is Br, Cl orcombinations of Br and Cl,

x is zero or 1,

y is 0, l or 2,

z is zero, 1 or 2, with the proviso that when 1 is zero, Q ishaloaryloxyalkyl or haloarylpolyoxyalkyl, and

thesum ofx+y+zis 3.

Compositions comprising an organic polymer and from about 2 to about 30percent by weight, based upon the weight of the compositions, are alsoprovided in accordance with the present invention.

As indicated, when w is zero, X is Br, or Br-Cl mixtures to assuresatisfying thennal stability for processing at high temperatures and/orgood retention during detergent washing. When w is 1, 2 or 3, however,the surprising advantages listed above are obtained when X is Br, C1 orcombinations thereof. Compounds of this invention wherein w is 1, 2 or 3are further advantageous as flame retardants in that no disagreeablephenolic odor is produced during burning of polymer compositions.Preferred compounds are those in which all halogen is bromine.

Within an individual haloalkoxyester group, when one R is CH, or CH X,the adjacent R is hydrogen.

Preferred ranges for number of carbon atoms for R groups are as follows:

alkyl C -C haloalkyl C -C (with l-3 alkoxy C -C aryl CsHs haloarylhalophenyl (with 1-5 halogen) arylalkyl C H CH and C H C H andparticularly preferred R groups are as follows:

alkyl CH and CH CH haloalkyl XCH alkoxy CH O and CH CH O It is alsocontemplated that mixtures of phosphites, mixtures of phosphates,mixtures of phosphonates, and mixtures of two or more thereof, arecontemplated herein.

halogen) SPECIFIC EMBODIMENTS The halogen-containing phosphoruscompounds of this invention can. be prepared by a variety of procedures.Preferred, however, is the procedure described in application Ser. No.789,404 for the preparation of halo-alkanol-halophenol mixtures,thereafter con verted to the desired phosphorus compounds:

wherein A is as defined below, X is bromine or chlorine, R"' is H, CH CHCH CH H or CH X; M represents the alkylene oxide adducts to thehaloalcohol; b is a number corresponding to about 0.5 times the numberof moles of A up to about a number equal to the number of reactivehydrogen atoms of A; c is the molar proportion of epoxide sufl'icing toremove small quantities of residual HX formed in the reaction when onlyb moles of alkylene oxide are used, and is generally from about 0.03 toabout 0.1 times b; the sum of d and e is about 1, and generally c isgreater than d when an unsymmetrical alkylcne oxide is employed.Further, may be considered to be the quantity of oxide required toreplace the quantity which reacts with the alcohol during the overallreaction.

The aromatic organic compounds shown above by A and which serve asreactants are represented by the general formula wherein: Ar representsan aromatic nucleus; R represents hydroxy, oxyalkanol, polyoxyalkanoland amino groups; and R represents alkyl, haloalkyl, hydroxyalkyl, aryl,haloaryl and halogen.

Preferred homogeneous aromatic groups Ar are phenyl and substitutedphenyl groups, such as Typical alkylene oxides or epoxides which can beused in forming the desired phosphorus compounds include: ethyleneoxide, propylene oxide, epichlorohydrin and epibromohydrin.

Typical halophenols, haloalkanols and halophenoxyalcohols for formingthe desired phosphorus compounds include: bromophenols;2,4-dibromophenol; bromoethanol; l-bromo2-propanol; chloroethanol;l-chloro-Z-propanol; 1,3-dibromo-2-propanol; 1,3- dichloro-2-propanol;l-chloro-3-bromo-2-propanol; 2(bromophenoxy)ethanol; and 2-(2,4-dibromophenoxy)ethanol; 2(chlorophenoxy)ethanol; and2-(2,4-dichloro)ethanol.

Representative phosphorus halides for forming the desired phosphoruscompounds, include: phosphorus trichloride and tribromide; andphosphorus oxychloride and oxybromide.

Mixtures produced from reaction 1) above have the followingcharacteristics:

a. AX,. is seldom a single product. When A is phenol and b is 2, themajor product, AX is 2,4-dihalophenol. Some monoand trihalophenols arealso produced.

b. When 12" is CH, or CH X, a mixture of primary and secondary alcoholsis produced usually in a ratio of about 30/70, respectively. Mixedprimary and secon dary phosphorus esters are produced from such amixture in subsequent reactions.

c. The concentration of M, alkylene oxide addition products of thehaloalkanols, is usually relatively small but always present.

d. A relatively small excess of alkylene oxide (up to 5l0 percent 12 inexcess of b c) can be employed if desired.

Aryloxy analogs of the halophenol, haloalkanol mixtures described abovecan be prepared in several ways. One method involves the use ofaphenoxyalkanol such as C H O(C H,O),H instead of phenol in the equationgiven above. (r is an integer from 1 to 3). A second method involves thereaction (2) indicated below:

KIA-OH btan cnxcmon eR CHOHCIhX) R!!! xbxocmenon b(dR"cHXcmo11 eRCHOHCHgX) CM cM' wherein M' represents additional alkylene oxidereaction products with the haloalkanols present and c represents themoles of alkylene oxide reacting to form M Mixtures produced fromreaction (2) have the following characteristics:

a. The characteristics of products from reaction l are equallyapplicable.

b. In most instances, only trace amounts of M are produced.

c. The preferred alkylene oxide for this reaction is ethylene oxide,although R can be CH or CH X.

d. The alkylene oxide generally is reacted with a phenol in a 1/1 molarratio.

The mixture produced in reaction (1) or (2) can be modified by addinghalophenols, halophenoxyalkanols, haloalkanols or alkanols thereto priorto formation of the desired phosphorus compounds. Such added compound orcompounds can be the same or different from those present in themixtures. EXAMPLE 1V provided below, illustrates this modification.Alternatively, a portion of the haloalcohol content of a mixture can beremoved therefrom, as by distillation, to achieve a desired ratio ofhalophenol or halophenoxyalkanol to baloalkanol.

Another alternative is to form a desired mixture ofhalophenol-haloalkanol or halophenoxyalkanolhaloalkanol by blending theindividual components. This alternative provides mixtures substantiallyfree of other compounds but is less economical than the proceduresrepresented by reaction (1) or (2).

Typical alkoxylated halogenated alcoholic mixtures include thefollowing:

J3r Br-OCH CH OH zaroanton I (I111: Br-OCH1CHOH ZBrCaHgOH c1 C1OCH;CH;OH20102114011 1 o1-o 01110112011 2c1o3m0n.

A mixed haloaryl, haloalkyl or haloaryloxyalkyl, haloalkyl phosphite canbe produced by reaction ofa phenol-alkanol or phenoxyalkanol mixturewith PX, using an acid acceptor, such as ammonia as shown by reaction(3a) W Wm R R R. R I 1 a aNm Xn 0 CH HO WH+ 2X HCHOH +PC1;

solvent 0* t t R Xn0 CHCHO .P(ocHeHx 3NH4C1.

Phosphites produced by this method are more complex than by the processsequence described below, because (a) the halogen/haloalkanol andhaloaryloxyalkanol/ haloalkanol mixtures usually contain a variety ofhalophenols, halophenoxyalkanols and haloalkanolsin rela 5 6 tivelysmall concentrations when made according to rel action 1) or (2), inaddition to the ma or components 1 thereof, and (b) statistically, it ispossible to form some Br tris(halophenyl), tris(halophenoxyalkyl) and/ortris(- haloalkyl)phosphites. 5 Br OPTOCHICHICOZ The phosphites soobtained can be converted to the corresponding phosphates andphosphonates as de- Br scribed below. These derivatives will be at leastas com- Br ocmcmoglocmcmcl) plex as the phosphite precursor. 1

Phosphites, phosphates and phosphonates of the C1 character used in thecompositions of this invention f can be prepared in excellent purity byusing the follow- 01- OCHICHzOPTOCIhCHICI) ing reactions: 2

B (a) r o u XFQOH PXa XFQOPXI HX BrocnicttioP ocnicmBr z B O r fl filBrQO-PNCHaCHzBr),

Br X OP[0CH(CHzX)R/]z Br- OPLOCH(CH1B1-)CH;] 1 phosphlte Br (o f (5)lNzO; heat catalyst a )z O P OCHICHIBI 2 The following representativecompounds can be formed by following the foregoing reaction sequences:

l BrOP(OCHzCHzCl) 40 Phosphates can also be produced directly by thetypi- Br cal reactions set forth below:

L 2 Compoundsproduced by the processes involving re- OCHZCHZOI, IOCnwmm)CH3] act|on (3a or react ons (7) and (8), are considered to L 2comprise average compositions with one or more major components. Typicalexamples are shown below in TABLE 1:

'r/lnim: l

An approximate 50-50 molar mixture of 4- bromophenol and Z-bromoethanolwas prepared by Molar rnllo ol' nlvolml rwr mol f l'X; or POX;

Added Ilnlnphenol Iluloalr-ohol alcohol Average structure Structure ofmajor com- (XArOlzPOdJHOHX pr nontl l Same.

Same.

(XArOhPO ,HCHk

plus

R l XArOP(Otl3HCHX)2 Same.

Combinations of halophenol and haloaleohol produced from reaction (1),above, are modified by adding or removing a halophenol or haloalcoholcomponent to provide the desired molar ratio.

The following examples illustrate the invention. Typical reactionconditions are provided in the examples.

EXAMPLE 1 Preparation of bis(2ch1oroethyl)2,4-dibromophenyl phosphiteOne third mole of 2,4-dibromophenol was melted and added to 1.5 moles ofphosphorus trichloride. The mixture was heated to reflux and the HClwhich formed was removed by nitrogen purge. After 3 hours, one third ofthe HCl had been removed as determined by titration with a base (aqueousNaOH). Magnesium chloride (0.003 mole) was added to the mixture, andrefluxing continued for 3 hours at which time 98 percent of HCl wasremoved. Excess PClIl charged was removed by heating to 45C. at 2 mmpressure to yield 104.9 grams (99.1 percent) of 2,4-dibromophenylphosphorodichlorodite with a purity of 94.3 percent as indicated by aVolhard chlorine analysis.

Ethylene oxide (0.65 mole) was added slowly to 0.3 mole of the abovephosphorodichloridite at a temperature below C. The resulting mixturewas allowed to stand at room temperature (about 20-25C.) for 48 hoursand was then stripped to remove excess oxide. A quantitative yield ofbis(2-chloroethyl)2,4- dibromophenyl phosphite was obtained having apurity of 95.0 percent by reaction with iodine, a density of 1.757 and11,7 of 1.5738. Elemental analysis gave 7.22 percent P and 73.3 percenttotal halogen as Br compared to theoretical values of 7.03 and 72.4percent, respectively. The product is identified hereinafter as Compound1.

EXAMPLE 11 Preparation of Mixture of bis(2-bromoethyl )4- bromophenyland bis(4-bromophenyl)Z-bromoethyl phosphites using phenol, bromine andethylene oxide. To a stirred solution of 1 mole of phenol and 0.55 moleof ethylene oxide was added simultaneously 1.0 mole of bromine and 0.55mole of ethylene oxide over a period of 30 minutes, while maintaining areaction temperature between 0-5C.

To 1 1 1.8 g of the above bromophenol, bromoethanol mixture dissolved in150 ml ethylene chloride was added 34.2 g of phosphorus trichloride overa period of forty-five minutes at 2 to 8C. while maintaining a pH of7-10 by simultaneous addition of anhydrous ammonia.

The resulting slurry was washed with 250 ml of 2 percent ammoniumhydroxide and the cloudy organic layer was separated and filtered. Theorganic layer was stripped to C. and 10 mm pressure. An 87.2 percentyield of the phosphite mixture was obtained. lodine titration of themixture showed 6.28 percent P compared to 6.52 theory. Elementalanalysis gave 6.87 percent P and 48.2 percent Br compared to theoreticalvalues of 6.52 and 48.6 percent, respectively, for a 5050 mixture of thetwo phosphites. The product is identified hereinafter as Compound 2.

Mixed phenyl or 2,4-dibromophenyl esters stemming from phenol and2,4-dibromophenol in the starting alcoholphenol mixture may beeliminated by starting with a 50-50 molar synthetic mixture of pure 4-bromophenol and 2-bromoethanol.

EXAMPLE lll Preparation of Mixture of bis(2-bromopropyl) 4- bromophenyland bis(4-bromophenyl)2-bromopropyl phosphite BrQ-O P10 cmcmancmh (Br-O)PoomcmBncm Compound 3 was prepared by the procedure outlined for Example11 except that methylene chloride was used as solvent and triethyl aminewas used as the acid acceptor. After washing with dilute ammoniumhydroxide, the organic layer was stripped to 100C. at 10 mm pressure. Anpercent yield of the phosphite mixture was obtained. Elemental analysisgave 5.78 percent P and 46.1 percent Br compared to theoretical valuesof 6.36 and 47.4 percent, respectively for a 50-50 molar mixture of thetwo phosphites.

EXAMPLE IV Preparation of butyl 2-bromopropyl 2-bromophenyl phosphiteBr-OP (o CHCH BICHa) omomcmom Compound 4 was prepared according to theprocess outlined for Example 111 except that 1.1 moles of nbutanol wasadded per mole of 4-bromophenol and bromopropanol prior to reaction withPCI pentane was used as solvent, and N11 was used as the acid acceptor.The mixed phosphite which was formed was separated by washing thepentane NH Cl-phosphite mixture with 2 percent ammonium hydroxide. Thepentane layer was separated and dried over sodium sulfate, decanted andstripped to 80C and 30 mm pressure. A 89.7 percent yield of thephosphite was obtained with a 7.27 percent P compared to 7.5 percenttheoretical. Elemental analysis gave 8.0 percent P and 34.8 percent Brcompared to theoretical values of 7.50 and 38.6 percent, respectively.

EXAMPLE V Preparation of bis(2-chloroethyl) 2,4-dibromophenyl phosphateThe phosphite of Example I was oxidized to Compound 5. Nitrogentetroxide, 2.6 g (20 percent molar excess), was added over a period ofminutes to 35.9 g of the phosphite of Example I dissolved in 35.9 ml ofmethylene chloride. The reaction temperature was maintained at 0 to l0C. throughout the addition. The temperature was allowed to rise toambient (2025C.). After standing for several days, the liquid productwas stripped on a rotary evaporator to 80C. at 5 mm pressure. A 99.5percent yield of the phosphate was obtained having c1 1.751, n 1.5572and an acid number of 18.1 mg KOH/g. Elemental analysis gave 6.64percent P and 69.2 percent halogen (as Br) compared to theoreticalvalues of 6.78 and 69.8 percent, respectively. The product is referredto hereinafter as Compound 5.

EXAMPLE VI Preparatio n of bis( 2-bromoethyl) dibromophenyl phosphateice bath, water reflux condenser and dry ice trap. Reaction temperaturewas maintained at 510C. throughout the addition. The reaction mixturewas stirred at 10-15C. for 30 minutes, then heated to 80C. and held atthis temperature for 6.5 hours while blowing with nitrogen to removehydrogen chloride. After cooling, 292.3 g of product was obtainedcompared to 291.1 g theoretical for bis(2-bromoethyl)phosphorochloridate plus unreacted 2,4-dibromophenol.

220 g of the phosphorochloridate mixture was removed and transferred toan addition funnel. Methylene chloride, 400 ml, was added to theremaining product. 28 ml (42.0 g) of 50 percent sodium hydroxide wascharged in a second addition funnel. The sodium hydroxide solution andphosphorochloridate were added simultaneously to the methylene chloridesolution of phosphorochloridate over a period of fifteen minutes whilemaintaining a reaction temperature of 513C. After addition was complete,another 3.9 g of 50 percent sodium hydroxide was added to raise the pHto 8-9.

After aging for one hour below 10C., 250 ml of 4 percent sodiumhydroxide and 300 ml of water were added and the organic layerseparated. The organic solution was washed again with 250 ml of 2percent sodium hydroxide followed by two 500 ml water washes. Theorganic layer was stripped to C. at about 25 mm pressure. An 89.7percent yield of bis(2-bromoethyl) 2,4-dibromophenyl phosphate wasobtained having N 1.5785, d 2.0 and an acid number of 0.08 mg KOH/g.Elemental analysis gave 5.75 percent P and 60.1 percent Br compared totheoretical values of 5.67 and 58.6 percent, respectively. The compoundis referred to hereinafter as Compound 6.

Alternate methods may be used to prepare this compound, one being theprocedure of Example 11 using 2,4-dibromophenol, PBr and ethylene oxidefollowed by oxidation with N 0 EXAMPLE Vll Preparation of bis(2-bromopropyl) dibromophenyl phosphate Compound 7 was prepared in asimilar manner as shown in Example V1 except that benzene was used assolvent. An 82.6 percent yield of the desired product was obtainedhaving d, 1.896, n 1.5755 and an acid number of 2.58 mg KOH/gm.

EXAMPLE VIII Preparation of tetrakis( 2-bromoethyl) tetrabromo(BisphenoLA) diphosphate mono [@omm 003.011.1301 2 EXAMPLE IX Preparationof Mixture of bis(2-bromopropyl) 4- hromophcnyl and bis(4-bromophenyl)2-bromopropyl phosphates Compound 9 was prepared by oxidation of thephosphite mixture of Example 111 according to the procedure of ExampleV. A near quantitative yield of the corresponding phosphate mixture wasobtained although about 20 percent of the phosphite remained as shown byiodine titration. The mixed phosphate also had 11 1.5601, df 1.657 andan acid number of 57.5 mg KOH/g.

EXAMPLE X Preparation of 2-chloroethyl 2-chloroethylphosphonate2,4-dibromophenyl BrQ-OZwwCmCmm HzCHzCl EXAMPLE XI Preparation ofphosphonate mixture from bis(2- bromopropyl) 2 (4bromophenoxy)ethyl) andbis[2-(4bromophenoxy)ethyl] 2-bromopropyl phosphite mixture oomcmancm Aphosphite mixture was prepared according to Example 11 using thereaction product of 1 mole phenol, 1 mole bromine and 1.2 molespropylene oxide and then ethylene oxide in Step 11 as in the followingEX- AMPLE X11. A 82 percent yield of the mixed phosphites was obtainedhaving r1 1.5603 and d 1.605. Elemental analysis gave 5.60 percent P and40.1 percent Br compared to theoretical values of 5.51 and 42.7 percent.respectively.

80 g of the phosphite mixture was isomerized by heating with 0.4 g 1 atl20-137C. for five and onehalf hours. The mixed phosphonate product hada p content of 0.03 percent, r2 1.5570 and elemental analysis gave 5.55percent P and 39.0 percent Br.

EXAMPLE Xll Preparation of bis( 2chloroethyl )2-( 2 ,4 dichlorophenoxy)ethyl phosphite Step I Preparation of chlorophenol, chloroethanolmixtures To a stirred solution of 3 moles of phenol and 0.45 mole ofethylene oxide was added simultaneously 1.0 mole of chlorine and 0.43mole of ethylene oxide over a period of 30 minutes, while maintaining areaction temperature between 388C. Since the reaction tended to freezeat temperatures below 15C., an additional mole of ethylene oxide wasadded, the mixture cooled to 0, and 4.4 additional moles of ethyleneoxide and 5 additional moles of chlorine were added simultaneously overa period of three hours, while maintaining a reaction temperature of 3to 5C.

Gas chromatographic analysis of the reaction product revealed (a)2,4-dichlorophenol and 2- chloroethanol as the major components, (b) 2-chlorophenol, 4-chlorophenol and 2,4,6- trichlorophenol as minorcomponents and (c) ethylene oxide and several ethylene oxide adducts ofchloroethanol as trace components. Step II Conversion of chlorophenolsin above mixture to 2(chlorophenoxy)ethanols To 947 g of the abovemixture containing about 2.88 moles of halogenated phenols in a 2 literpressure apparatus was added 4.05 moles of ethylene oxide and 1.1 g ofsodium formate. The mixture was heated with stirring to 103C. over aperiod of 1 hour and 50 minutes at which point a maximum gauge pressureof 48 psi was observed. Heating was continued for about 4 hours to C.during which time the pressure continued to drop until 37 psi gaugepressure was observed at the end of this heating period. An additional 1hour and 45 minutes heating period at 120C. failed to further reducegauge pressure. A golden yellow liquid product was obtained in nearquantitative yield.

Gas chromatographic analysis of the unstripped product revealed onlytraces of the original phenols and an excess of ethylene oxideapproximately equal to 0.5 moles excess ethylene oxide per mole oforiginal phenol. The major components were chloroethanol and2(2,4dichlor0phenoxy)ethanol. Minor quantities of the ethylene oxideaddition products of 2,4,6- trichlorophenol, 2-chlorophenol,4-chlorophenol and ethanol were also found. Step III Formation ofphosphite from above mixture To a 1 liter, 7-neck round-bottom flaskequipped with stirrer, thermometer, pH meter probe, 2 addition funnels,nitrogen purge tube, ammonia bubbling pipe and dry ice bath was added 10g of the mixed alcohol product from Step 11 and 256 g of ethylenechloride. Phosphorus trichloride (0.25 mole) was added to one of theaddition funnels and diluted to 60 ml with ethylene chloride. To theother addition funnel was added 85.7 g of the mixed alcohol product fromStep II and diluted to 120 m] with solvent.

After cooling the contents of the flask to 2C., ammonia was bubbled inuntil a pH of 9.0 was observed. The PCI and alcohol mixture were addedsimultaneously over a period of about 20 minutes while maintaining (a) abalanced flow (molar quantities) of PCl and alcohol mixture (b) a pH of8.5-9.0 and a reaction temperature of 3C. 400 ml of 3 percent ammoniumhydroxide was added to the slurry and after agitation to dissolve theammonium chloride, the organic layer was separated and stripped to 25C.at 10 mm pressure. A 94.6 percent yield of the phosphite was obtainedhaving an acid number of 1.6, 11 1.396 and 11 1.5371. Iodine titrationshowed a purity of 80.0 percent. This compound is identified as Compound12.

EXAMPLE X111 Preparation of bis( 2-chloropropyl 2-( 2,4-dichlorophenoxy) ethyl phosphite 683g (0.33 mole) of2,4-dichlorophenoxyethanol was added to 226.6 g (1.65 moles) ofphosphorus trichloride at 5C. over a period of about ten minutes.Stirring and cooling was applied during this period to maintain areaction temperature of 57C. After removal of the ice-bath, thetemperature rose to 25C. over a period of one and one-half hours. Heatwas applied over the next two and one-half hours to maintain a reactiontemperature of 758 1C. The evolving l-lCl was absorbed in water and 104percent of theory was evolved.

After standing overnight, the excess PC];, was stripped up to 45C. and 2mm pressure. 99.6 g of the light yellow 2,4-dichlorophenoxyethylphosphorodichlorodite was obtained corresponding to a 98 percent yieldbased on 2,4-dichlorophenoxyethanol. Gas chr0- matographic analysis ofthe phosphorodichlorodite showed only traces of PCl and thephenoxyethanol. Purity by the Volhard method was 94.3 percent.

Propylene oxide, 0.97 mole, was added to 0.32 mole of the abovedichlorodite in a 250 ml flask equipped with a stirrer, thermometer,addition funnel, dry ice condenser and ice bath over a period of 30minutes while maintaining a reaction temperature of 14-20C. A reactiontemperature of l625C. was maintained over a period of two hours.

After standing overnight, the product was stripped to 80C. at 10 mm.134.4 g of the light yellow, bis(2-chloropropyl)2,4-dichlorophenoxyethyl phosphite was obtainedcorresponding to a yield of 98 percent based on phosphorodichlorodite.Gas chromatographic analysis showed the presence of only a trace oftris(2- chloropropyl)phosphite. Elemental analysis gave 7.33 percent Pand 34.4 percent Cl compared to 7.30 percent P and 33.4 percent Cl,respectively. Iodine titration showed a purity of 96.5 percent. Adensity, d of 1.258 and an index of refraction at 25C. of 1.5299 werefound. This compound is identified as Compound 13.

EXAMPLE XIV Preparation of bis( 2-chloropropyl)2-(2,4- dichlorophenoxy)ethyl phosphate Nitrogen tetroxide, 2.9 g (20 percent molar excess), wasadded over a period of 10 minutes to 39.3 g of the phosphite of EXAMPLEX111 dissolved in 39 ml of methylene chloride. The reaction temperaturewas maintained at 0 to 10C. throughout the addition. The temperature wasallowed to rise to ambient. After standing for several days, the liquidproduct was stripped on a rotary evaporator to C. at 5 mm pressure. A 97percent yield of the phosphate was obtained having (1 1.336, 11 1.5189and an acid number of 18.0 mg KOH/gm. Iodine titration gave 0.6 percentP Elemental analysis gave 6.97 percent P and 29.8 percent Cl compared totheoretical values of 7.04 and 32.2 percent, respectively. This compoundis identified as Compound 14.

EMPLE XV Preparation of tetrakis(Z-chloroethyl) tetrachloro(Bisphenol-A) diphosphite nac o Qomocmomom Compound 15 was preparedaccording to the procedure of EXAMPLE X11. After washing the slurry with3 percent ammonium hydroxide followed by a second wash with 3 percentsodium hydroxide, the resulting organic layer was stripped to C. at 10mm pressure. A 78 percent yield of the white, waxy solid was obtained. AP and P analysis gave 7.12 and 0.93 percent, respectively, compared to atheoretical total phosphorus value of 8.31.

EXAMPLE XVI Preparation of bis( 2-chloropropyl 2-( 2 ,4-dichlorophenoxy)-ethyl phosphonate Compound 16 was prepared by heating40.3 g of the phosphite of Example Xlll with 0.2 g 1 at l20l25C. for 2hours and l50l55C. for 13 hours. After stripping to 124C. at 10 mmpressure, a 89.8 percent yield of the corresponding phosphonate wasobtained having (1 1.404, n,, 1.5291, and an acid number of 2.8 mgKOH/g. Elemental analysis gave 7.69 percent P and 32.61 percent Clcompared to theoretical values of 7.30 and 33.4 percent, respectively.

POLYMERIC MATERIALS The polymeric materials employed in the compositionsof this invention can be natural, regenerated or synthetic. Includedamong natural materials are: cotton, cellulose, paper and silk.Regenerated polymers include: viscose rayon and cuprammonium rayon.Typical synthetic materials include: cellulose esters and ethers, suchas acetate rayon, cellulose acetate butyrate and ethyl cellulose;polyvinyl chloride; polyurethanes; polycarboxamides of the nylon type;polyacrylonitrile;

ll polyethylene; polypropylene; polystyrene; alkyd resins; urea resins;polyisobutylenes; polymethyl methacrylates; phenol aldehyde resins;linear and cross-linked polyesters; maleic anhydride heteropolymers;styrenemethacrylate copolymers.

While improvement in flame resistance and excellent retention isafforded by incorporating the phosphorus compounds of this invention ina wide variety of polymers, the preferred polymers are cellulosics (suchas viscose rayon, acetate rayon, cellulose acetate butyrate),polystyrene, polyurethanes, polyvinyl chloride, polyethyleneterephthalate polyesters, polyolefins and polyacrylonitrile.

One or more of the compounds of this invention provide excellent flameproperties in combination with most natural, regenerated and syntheticpolymer systems.

It is to be noted that while all compounds of this invention aresusbstantially superior to known flame retardants such as tris(haloalkyl) phosphates and his (haloalkyl) halo-alkyl phosphonatesregarding resistance to detergent washing of acetate rayon compositionsas shown below in TABLE 11, the same does not apply for all polymercompositions For example, Compound 6 was found superior inpolyacrylonitrile, as other compounds of this invention (as well as thetris (haloalkyl) phosphorus derivatives) are lost during detergentwashing. Conversely, almost all polystyrene, polyvinyl chloride andcellulose acetate butyrate films containing either compounds of thisinvention or known flame retardants retained their flame resistanceafter detergent washing by our standard procedure. It is believed,however, that the retentive properties of compounds of this inventionwould be superior to conventional flame retardants such as thetris(ha1o-alkyl) phosphates in most polymer systems provided theexposure time is decreased in the case of polyacrylonitrile or increasedin the case of the more hydrophobic polymers such as polystyrene,polyolefin, PVC, etc. Most of the compounds of this invention possessunusually high stability for high temperature processing, and are stableto detergent washing in most polymer systems.

The physical form of the polymer-phosphoruscompound composition can varywidely. While textile fibers are of major interest, films, coatings,sheets, rods, boards, and the like can be used. Excellent retention offlame resistance is achieved when the flame retardant is distributedrather uniformly throughout the polymer; however, surface treatments arealso advantageous.

One or more of the phosphorus compounds described herein can beincorporated in the polymer during the polymerization step or byadmixing with the polymer prior to or during milling, extrusion,spinning, foaming or other conventional operations used for forming orapplying the polymeric end product.

POLYMERIC COMPOSITIONS Representative halogen-containing phosphoruscompounds have been incorporated in one or more polymer systems at oneor more concentrations.

EXAMPLE XVII Results of flame tests made with a number of compositionscomprising an acetate rayon (cellulose acetate) and a halogenatedphosphorus compound are provided below in Table II. The rayon employedwas in the form Three or more /2 inch X 2 inch samples were cut fromeach film composition. Each sample was folded with creasing along the 2inch axis to form a V shape (end view) whereby each side of the V wasapproximately A inch and the angle formed by the sides of the V wasapproximately 90. One end of the sample was placed in a single clamp insuch a manner that the free end could be ignited with a paper match.

Samples of each composition were tested in one or more of the positionsas defined below:

Path of Flame Propagation after Ignition Position of Free End 0 downwardand to horizontal 45 downward at 45 to horizontal 90 horizontal upwardat 45 to horizontal upward at 90 to horizontal The flame was applied for2 seconds at the bottom point of the V of the free end and removed. Ifthe flame progressed to the clamp, the sample was considerednon-self-extinguishing (NSE) in that position. If the sample wasself-exinguishing (SE) before the flame reached the clamp, the flame wasapplied for another two seconds. If the sample was SE before reachingthe clamp after the second ignition it was considered SE in thatposition.

Generally, the first sample of each film composition was tested in the90 position. lfit was found to be NSE at 90, additional samples weretested sequentially in the 45 and 0 positions. If the second sample wasSE at 45, this was considered the maximum angle whereby the sample wouldbe found SE and recorded as such. If however, the first sample tested inthe 90 position was found to be SE, additional samples were testedsequentially in the 180 and 135 positions. For clarification of flameproperties ratings in Table II and subsequent tables, the table belowrates flame properties as assessed in individual positions and overallrat- Positions Tested (Performance) Overall Rating 90 (NSE), 45 (SE) 4590 (NSE), 45 (NSE), 0 (SE) 0 90 (NSE), 45 (NSE), 0 (NSE) NSE90(SE),180(SE),135(SE) 180 90 (SE), 180 (SE), 135 (NSE) 180/90 90 (SE),180 (NSE), 135 (SE) 135 It is to be understood that flame resistancevaried proportionately to the numerical value assigned for the overallrating (corresponding to the position as defined above). Thus, flameresistance is greatest with a value of 180, and least with a value ofNSE. The data in Table II shows the excellent improvement in flameresistance provided by the halogen containing phosphites, phosphates andphosphonates compared to the control.

TABLE II.ACETATE RAYON. FLAME RETARDANI COMPOSITIONS Flame properties at8% loading, 4% loading, Compound 16% loading, before before numberStructure before /aiter b after b after b PHOSPHATES 7BI2QSOP(O)|OCH(CH2B1')CH3]2 180/90 180/45 ISO/NSE Br2OP(O)(OC2H4Br)g180/180 180/180 180/135 (BrCHzCHzO):P(O) IBO/NSE 180/NSE ISO/NSE 8 I" B!45/45 0/0 0/0 (cubic-Q0 P o (0 (3211,1302

Br2OP(O)(OC2H4Cl)z 180/45 180/0 IRO/NSE 14 01 180/35 180/0 180/0 oiocmcmopto) (0 camel).

(ClCzH4O)aP(O) 180/0 180/NSE 135/NSE PHOSPHONATES BH SOPUJOCzHlCI 180/45180/45 180/0 H2CH2CI 16 Cl OCH CH PO(OC3H0CI)2 180/0 90/0 180 0 BroHzoriiPdwomcmBm 180/NSE ISO/NSE ISO/NSE PHOSPHITES 1 Br OP(OC2H4Cl)z /045/NSE 4.5/NSE 13 Cl2 0CyH4OP(OC3HuCl)2 45/NSE OINSE OINSE l Beforedetergent washing.

b After detergent washing. No'rE.-Contre1 (no flame retardant added)=NSE.

The flame properties of film compositions were also determined afterwashing 2 inch X 8 inch film strips in water containing a typicallaundry detergent at 80C. for four hours. Ten film strips were washed atone time by combining the strips in a bundle composed of alternatinglayers of a 2 inch X 6 inch screen wire (/1 inch mesh) strips, 1 inch X2 inch cardboard strips at one end (serving as 4; inch spacer), and thefilm strip. The bundle was immersed into a heated water bath (80C.) to adepth of about 6 inches and 4 inches with respect to the film strips andscreen wire strips, respectively. The bundle was supported by two large3-pronged clamps by closing the clamps across the top end of the bundlewith the cardboard spacers. Clamp pressure was applied across thecardboard spacers in such a manner that the bottom of the bundle wasspread to allow about inch distance between each screen wire strip.

About 2 liters of water was used for each bundle. The water was stirredby means of a magnetic stirrer and contained 12.5 g of detergent withthe compositions as follows:

10.0 pts. Alkylphenoxypoly(ethyleneoxy)ethanol 5.0 pts. Sodiumdodecylbenzene sulfonate 35.0 pts. Sodium tripolyphosphate 10.0 pts.Borax 5.0 pts. Sodium metasilicate 33.5 pts. Sodium carbonate.

After a 4 hour wash period, the film strips were thorand all 11 which isincluded for comparative purposes.

TABLE IIA ACETATE RAYON FLAME RETARDANT COMPOSITIONS EXAMPLE XVIII Filmswere cast from a 10 percent solution of polyacrylonitrile in dimethylformamide containing 8, 16 percent and 24 percent (based on weight ofpolymer plus flame retardant) of the phosphorus-halogen compounds asshown in Table III. The polyacrylonitrile used was in the form ofknitting yarn identified as percent ORLON. The films were dried for 20minutes in a forced draft oven at l05-1 10C., stripped, heated for anadditional hour at C and allowed to condition for 24 hours at 73F., 50percent relative humidity before testing. Film thickness wasapproximately 1 mil, lms including the control were hazy.

The flame properties of each film were determined as described above inconnection with the rayon compositions. The results are summarized inTable III.

TABLE IIT.POLYACRYLONITRTLE. FLAME REIARDANT COMl'ORlIlONS Flameproperti at- 24% 16% 3% Compound number Structure loading loadingloading PHOSPHATES 7 BmSOPtO) (OCfl'TaBUz 45 45 NSE 6. .A Br:OP(0l (C2HBl): 45 45 0 5 Brzd OP(O) (OCzHiCl-2 45 0 NSE 14 C12OCH2CPI2OP(O)(OCaHoClal 45 0 NSE 8 t i 0 NSE Br (CH1)zC--OP(O)(0C H Br) PHOFPHA'IESl0 BrOP(O)(OCHzCHzCl) 45 0 NSE HzCHzCl l6 Clzd OCHzCH2P(O)(OCaHuCl): 0 ONSE PlIOSllllTES i llrwOHOCflhClh 90 4h 45 s (H t/AH;ll; 7ll filflVgll'nl a 45 45 NHIC No'Hz-(ontrol (no flame retardant added)-=NSF..

EXAMPLE XVIX TABLE IV a sulfuric acid bath, the film was washed anddried at elevated temperatures. The films were conditioned at 73F,percent relative humidity for at least 24 hours prior to testing.

The flame resistance of each rayon-flame retardant film composition wasdetermined as described above in regard to the rayon compositions above.The film compositions were analyzed for phosphorus and halogen to assessthe retention of flame retardant after film prepa' ration. These resultsare shown in Table V.

It is to be noted that the capture and retention of the compounds ofthis invention is substantially greater CELLULOSE ACETATE BUTYRATE.FLAME RETARDANT COMPOSITIONS Flame Properties At Compound Structure l67zloading 8% loading 49? loading 27: loading Number PHOSPHATES 7 Br. .dOP(O) (OC H Br) 180 180 180 6 Br qbOPtol (OC HJBU 180 135 90 5 Br-,OP(O) tOC,H,CI) l 180 ISO l4 CI:OCH CH OP(O) 135 45 (OC H CUPHOSPHONATES ltl Br OP(O)OC H Cl I80 I80 90 CH CHA Cl It CI QSOCH- CHPtO) (OC H CU 135 45 PHOSPHITES l Br aSOPtOc H Cll 45 45 45 13 (l dioCHCH OlN OC H CI NSF. NSE 45 NoTE.(ontrol (no llame retardant addedl=NSEEXAMPLE XX Viscose rayon films were cast from cellulose xanthatesolutions containing one or more levels of the compounds shown in TableV. These compounds were dispersed in a xanthate solution at levels of1.0 percent TABLE V.VISCOSE RAYON FLAME RETARDANT COMPOSITIONS Percentloading Flame Compound number Structure Theory Found rating PHOSPHONATES(Br OCHZCH ))ZP(O)C3HOBI plus 27. 2 21. 2 90 Br 0CH OH;O1|(O OCaHBrcaHtBr (BrCaHsOl PwwaHiBr 21. 5 8. 6 45 PHOSPHITES 3 BrOP(OC3HaBr)z 15.7 14. 4 90 plus (BI'O)2POCBHOBF 23. 4 18. 3 90 4BrOPlOCH(CHzBr)CH3](OBU) 13.4 11.7 45 20.0 13. 8 45 (BrCzH)3P 19. 5 4.1NSE (BrCzlIaOhP 21.0 1.7 NEE (Clbflhohl 13. 0 (1.7 NBE Nora-Control (noflame retardant added) =NSE.

EXAMPLE XXI Films were prepared from a 10 percent solution ofpolystyrene in benzene containing 4, 8, l6 and 24 percent of thecompounds as shown in Table VI based on the total solids weight ofpolystyrene and phosphorushalogen compound. The polystyrene sample wasobtained by dissolving polystyrene foam in benzene. After drying the wetfilms at 50C. for minutes, the dry films were stripped and conditionedat 73F, percent relative humidity for 24 hours. The flame properties ofthe films were determined according to the test procedure given foracetate rayon films given above. The results are shown in Table VI.

The flame properties were determined on each composition as describedabove except that the sample used for flame test was prepared by cuttinga 1 inch X 2 inch strip and folding twice to make a 54 inch X 2 inchTABLE VI POLYSTYRENE. FLAME RETARDANT COMPOSITIONS Nona.-(lonlrol (noflame retardant uddcdkNSF.

EXAMPLE XX test strip. This modification was necessary to provideadequate rigidity of the film sample to be self supporting at therequired test angles. The results are tabulated in Table Vll.

Films were prepared from a methyl ethyl ketone solution of 8.8 percentpolyvinylchloride (PVC; GEON TABLE VII.POLYVINYL CHLORIDE, FLAMERETARDAN'I COMPOSITIONS Flame properties at- Compound 167 87 4 2 numberStructure loading loading loadlri g loadiri g PHOSPHATES 7Br2OP(O)(OC3HaBr)z 180 180 135 6... Br:OP(O)(OCzH4Br)2 180 180 180 5.BrzOP(O)(OCzH4Cl)2 180 180 135 14 ClzqSOCzII4OP(O)(OC3HeCl)z 180 90 90PHOSPHONATES BrzOP(O)OCzH4C1 180 180 180 CHzCHzCl 16CI2OC2H4P(O)(OC3H6CI)2 180 90 90 N orE.Contro1 (no flame retardantadded)rated 45.

EXAMPLE XXIII EXAMPLE XXV Polyethylene terephthalate polyester (Averagemo- A i id polyurethane f was r p r d f m Comlecular weight of 40,000),flame retardant film compopound 2 sitions were prepared by adding 0.2,0.4 or 0.8 g of the halogen-phosphorus compounds shown in Table VIII and4.8, 4.6 or 4.2 g of polyester chips, respectively, to a 14 X 120 mmtest tube. After heating the test tube in a Bunsen flame until thepolyester flowed freely (about 250300C.), a 3/8 inch X 6 inch strip ofaluminum screen wire was inserted and used as a stirrer to thoroughlymix the molten polyester and flame retardant, the test tube was thentilted and the polyester, flame retardant mixture was allowed to runonto and penetrate the screen wire strip to a distance of 3-4 inches.The mixture quickly solidified on the wire upon removal from the testtube leaving a continuous film (coating) over the entire wire surface.

The flame resistance of the strips were determined according to theprocedure given for acetate rayon films except (a) the coated wire stripwas not folded and (b) an ignition time of 10 seconds was employed.

The flame ratings obtained are shown in Table VIII. The high degree ofthermal stability shown by some of these compounds, especially Compounds6 and 10, is of major significance.

TABLE VIII a. A semi-prepolymer was prepared by adding 2.5 parts of asucrose polyether polyol having a hydroxyl number of 441 mg KOH/gm(prepared from propylene oxide and sucrose) to 97.5 parts ofpolymethylene polyphenylisocyanate preheated to -80C. The ad duct washeated for one hour at 90C. The semiprepolymer was found to have an NCOcontent of 29.5 percent.

The polymethylene polyphenylisocyanate used above is a mixturerepresented by the formula:

IIICO I NCO IIICO L"\/ to POLYETHYLENE TEREPHTHALATE POLYESTER, FLAMERETARDANT COMPOSlTlONS Compound Structure Flame Properties A!Nora-Control (no flame retardant added)rated 90. a. discolorationoccurred during sample preparation b. decomposition too severe duringsample preparation to warrant testing 1:. slight discoloration occurredduring sample preparation EXAMPLE XXIV while maintaining a temperatureof 94-l 20C. At the end of the propylene oxide addition, a pressure of92 psi was recorded at a temperature of 122C. The prodnot was aged for 2hours at 122126C. with a final pressure of 88 psi at 126C. After ventingand stripping at 128C. and 7 mm pressure to remove excess propyleneoxide, 658 parts of polyester polyol was obtained having a hydroxylnumber of 368 mg KOH/gm and an acid number of 0.125 mg KOH/gm.

A sucrose-polyether polyol-polyethylene glycol blend was prepared byadding 7.5 parts of polyethylene glycol, molecular weight 200, and 7.5parts of polyethylene glycol, molecular weight 300, to 85 parts ofasucrose polyether polyol (prepared by adding 8.7 moles of propyleneoxide to 1 mole of sucrose) preheated to 8090C. followed by stirring.

54.6 g of the sucrose polyether polyol-polyethylene glycol blend wasthoroughly mixed with 54.6 g of the polyester polyol above, 48.0 g ofCompound 2, 2.4 g of 3 was used. The resulting rigid foam also ratednonburning by ASTM D-1692-59T.

EXAMPLE XXVI Another rigid polyurethane foam was prepared by blending24.3 parts of a sucrose polyether polyol, hydroxyl number of410 mgKOH/gm, 4.0 parts ofa silicone oil surfactant, 4.0 parts of N, N, N, N-tetramethylbutane-l,-3-diamine, 99.5 parts of trichlorofluoromethane and107.5 parts of bis(2-bromoethy1) 2,4-dibromophenyl phosphate (Compound6). 250 parts of the semi-prepolymer of EXAMPLE XXV was then added,followed by vigorously mixing. At the onset of foaming, the mixture waspoured into a cardboard box and allowed to rise and cure at roomtemperature. A foam was obtained having a density of 2.24 pounds percubic foot.

Two additional foams were prepared in a similar manner using thecalculated quantity of the above phosphate to produce urethanecompositions containing 0.5 and 0.25 percent P based on totalformulation weight excepting trichlorofluoromethane. Thetrichlorofluoromethane was adjusted to 14.0 percent in each compositionto provide a constant density of about 2.2 pounds per cubic foot.

The flame properties of rigid foams containing Compound 6 as determinedby ASTM D-1692 59T are shown below.

The rigid polyurethane foams containing Compound 6 also showed excellentdimensional stability in accelerated heat and heat-moisture tests.

EXAMPLE XXVlI A flexible polyurethane foam was prepared from the recipeas shown below:

Ingredient Parts by Weight Toluene diisocyanate (TDl) 135.4 Polyethcrtriol (MW approx. 3000) 300 Compound 6 53.3 Silicone oil surfactant 3.0Stannous oetoate 0.9 N,N'-Dimethyl ethanolamine 1.2 Water 10.6

All of the ingredients above except toluene diisocyanate percent,2,4-isomer; 20 percent 2,6-isomer) were blended at room temperature(about 20C.). The diisocyanate was then added, mixed vigorously forabout 12 seconds and the mixture was poured into a cardboard box andallowed to foam. After full rise had occurred, the foam was placed in anoven at C. for 30 minutes. After removing to crush closed cells bymechanical compression, the foam was heated for an additional 2 hours at120C. The foam was found to have a density of 1.98 pounds per cubic footand contained 0.6 percent P based on total formulation weight.

Two additional foams were made in a similar manner except that theconcentration of Compound 6 was varied to provide phosphorusconcentrations of 0.3 and 0.2 percent, respectively.

The flame properties of these three foams as measured by ASTM D-1692-59Tare shown below:

Flame Properties P in Composition Inches Burned Rating 0.6 0.94non-burning 0.3 1.5 self-cxling. 0.2 3.1 self-exting. 0.0 6.0 burningThe halogen-containing phosphites, phosphonates and phosphates of thisinvention are useful as flame retardants in polymer systems as shownabove. Phosphates are preferred over the phosphonates or phosphites asflame retardants. The processes of manufacture utilizing the mixedhalopehnol-haloalkanol or halophenoxyalkanolhaloalkanol mixtures arepreferred owing to lower cost products.

What we claim is:

l. A composition comprising an organic polymer and from about 2 to about30 percent by weight, based upon the weight of the composition, of acompound selected from the group consisting of R R' R R (X tHtHO). POtHtH .0

(QM: (XL: Z

Q o X R 0 Q 43 xcrrcno I a" OCHCHX I I X x R R R R and mixtures thereof,

wherein X is bromine or chlorine,

R is H, CH or CH X, provided that when one R is other than H, theadjacent R is H,

R is X, alkyl, haloalkyl, alkoxy, aryl, haloaryl or arylalkyl, whereinhalo is X, R is H or CH Q is OCHCIJHX, (JHCIIDL R R R R or haloarylthesumofX+y+z is 3.

2. The composition defined in claim 1, wherein the compound comprises aphosphite.

3. The composition defined in claim 1, wherein the compound comprises aphosphate.

4. The composition defined in claim 1, wherein the compound comprises aphosphonate.

5. The composition defined in claim 1, wherein X is chlorine.

6. The composition defined in claim 1, wherein X is bromine.

7. The composition defined in claim 1, wherein the compound isbis(2-chloroethyl) 2,4-dibromophenyl phosphite.

8. The composition defined in claim 1, wherein the compound isbis(2-chloropropyl)2-(2,4- dichlorophenoxy) ethyl phosphite.

9. The composition defined in claim 1, wherein the compound isbis(2-bromothyl)2-(2,4- dibromophenoxy)ethyl phosphate.

10. The composition defined in claim 1, wherein the compound is bis(2bromoethyl)2,4-dibromophcnyl phosphate.

11. The composition defined in claim 1, wherein the compound is2-chloroethyl 2,4-dibromophenyl Z-chloroethylphosphonate.

12. The composition defined in claim 1, wherein the polymer iscellulosic.

13. The composition defined in claim 1, wherein the polymer is viscoserayon.

14. The composition defined in claim 1, wherein the polymer is celluloseacetate.

15. The composition defined in claim 1, wherein the polymer is anacrylonitrile polymer.

16. The composition defined in claim 1, wherein the polymer is a vinylpolymer.

17. The composition defined in claim 1, wherein the polymer is apolyurethane.

18. The composition defined in claim 1, wherein the polymer is a naturalpolymer.

19. The composition defined in claim 1, wherein the polymer is apolyolefin.

20. The composition defined in claim 1, wherein the polymer is apolyester.

21. A composition of claim 1, wherein w is l, 2 or 3.

, 6 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent NO 5 9I ated Q Inventoflg) James J. Anderson et al. i i

It is certified that error appears in the above-identified patent andthat id et ntsssbsrshv EPIKQQEQE?fih nlbf lp Cover Page, Section[60]"Sept. l9 1969" should be ---Sept.' l, l969--. Column 2, line 61, "CH Hshould be ---C6H5--. Column 16, line 17, "the v was? should be --the "vv p p wa's--. I Column 16, line 19, v the V was" should be -the "V"was-'.

Column 16, line 3A, "the v was" should be --the "v" of Table 3, Compoundl -L, 7 I "(O0 H6012 should be Table 3, after Compound '8, "PHOSPHATES"should be --PHosP1-l0NATEs--., Table l, Compound 10, "Br OP(O OC2HL ClCHgCHgCl should be CH CHgCl Table 5, Compound 11, "OCH-120E123 should b-OCH2CH2O Table 6, Compound 10, "Br2Q5OP(O)OC2HllCl 011 011 01 should be--Br oP(o)0c H ol s CH 011 01". .Table 8, Compound 10, "Br2Q5OP(O$OC2HLCl v CHgCHgCl should be ---Br o1 (0)oo 1{ cl- 011 0111 01, Column 23,line 69, "6, compared should be --6,

s respectively, compared--. Column i 55, "(Q) should be -(Q,) molumn 28,line 7', "bromothyl" should be -bromoethyJJ--.

Signed and sealed this 5rd day of December 197 (SEAL) Attest:

Commissloner of Patents FORM po 1o50u0 69) USCOMM-DC 60376-P69 U.SGOVUINMENT PRINTING OFFICE I 59. 930

esting Officer

2. The composition defined in claim 1, wherein the compound comprises aphosphite.
 3. The composition defined in claim 1, wherein the compoundcomprises a phosphate.
 4. The composition defined in claim 1, whereinthe compound comprises a phosphonate.
 5. The composition defined inclaim 1, wherein X is chlorine.
 6. The composition defined in claim 1,wherein X is bromine.
 7. The composition defined in claim 1, wherein thecompound is bis(2-chloroethyl) 2,4-dibromophenyl phosphite.
 8. Thecomposition defined in claim 1, wherein the compound isbis(2-chloropropyl)2-(2,4-dichlorophenoxy) ethyl phosphite.
 9. Thecomposition defined in claim 1, wherein the compound isbis(2-bromothyl)2-(2,4-dibromophenoxy)ethyl phosphate.
 10. Thecomposition defined in claim 1, wherein the compound is bis(2bromoethyl)2,4-dibromophenyl phosphate.
 11. The composition defined inclaim 1, wherein the compound is 2-chloroethyl 2,4-dibromophenyl2-chloroethylphosphonate.
 12. The composition defined in claim 1,wherein the polymer is cellulosic.
 13. The composition defined in claim1, wherein the polymer is viscose rayon.
 14. The composition defined inclaim 1, wherein the polymer is cellulose acetate.
 15. The compositiondefined in claim 1, wherein the polymer is an acrylonitrile polymer. 16.The composition defined in claim 1, wherein the polymer is a Vinylpolymer.
 17. The composition defined in claim 1, wherein the polymer isa polyurethane.
 18. The composition defined in claim 1, wherein thepolymer is a natural polymer.
 19. The composition defined in claim 1,wherein the polymer is a polyolefin.
 20. The composition defined inclaim 1, wherein the polymer is a polyester.
 21. A composition of claim1, wherein w is 1, 2 or 3.